Phosphorescent, fluorescent and reflective coated sheets or films and compositions and method for making the same

ABSTRACT

Phosphorescent and fluorescent coated sheets and films and coating compositions and methods for making the same in which the coating compositions include a solid phase embodying a phosphorescent pigment and/or fluorescent pigment phase and a socalled hot melt coating or vehicle for the pigment. The coating compositions are applied to a carrier or base sheet by a continuous coating operation, at an elevated temperature, following which the coating composition is transferred from the carrier or base sheet to a polyester or like film, or to a paper sheet or woven fabric, on which it is carried to complete the phosphorescent and/or fluorescent coated film. The phosphorescent products are useful as label stock, highway warning signs and road stripes, identification tapes, which glow at night, on tags, games, clock faces, instrument dial faces and for other purposes and the fluorescent products are useful in the graphic art fields and elsewhere. The continuous coating operation is much more rapid than prior art processes and avoids the use of highly volatile solvents employed in that process and the industrial pollution and other hazards thereto, as well as the extended drying time of the solvents which is required in the use of such prior art methods. Finely divided light-reflective particles, such for example, as glass beads, aluminum foil chips, metal powders and colored plastic resinous particles may also be incorporated in the new coated sheets or films by application to the hot melt coating while the latter is in a soft condition to enable the finely divided reflective particles to adhere thereto.

nited States atent [191 Cornell et a1.

[ 1 Mar. 25, 1975 PHOSPHORESCENT, FLUORESCENT AND REFLECTIVE COATED SHEETS OR FILMS AND COMPOSITIONS AND METHOD FOR MAKING THE SAME [76] Inventors: Richard K. Cornell, 2880 Duffy Ln.,

Deerfield, 111. 60015; Gerald J. Deddo, 513 Saint Charles Road, Elmhurst, 111. 60126; Henry L. Gianatasio, 1543 North Franklin, River Forest, 111. 60305 [22] Filed: Sept. 27, 1972 [21] Appl. No.: 292,552

[52] US. Cl. 156/230, 106/288 B, l17/33.5 R, 117/33.5 T, 117/68.5, 117/119.2, 156/293, 156/301,156/238 [51] lnt. Cl. 1344c 1/16 [58] Field of Search 117/33.5 R, 33.5 T, 68.5, 117/235, 119.2; 156/230, 344, 293, 301, 238; 106/288 B [56] References Cited UNITED STATES PATENTS 2,292,914 8/1942 Wesch l17/33.5 R 2,798,821 7/1957 Lehmann ll7/33.5 R 2,799,609 7/1957 Dalton 117/235 2,949,382 8/1960 Dickerman et al..... l17/33.5 T 3,115,417 12/1963 Christensen 117/33.5 R 3,253,148 5/1966 De Vries 1l7/33.5 R 3,518,205 6/1970 Vukasovich 117/335 R 3,679,234 7/1972 Colliau 1l7/33.5 R 3,788,879 l/l974 Waysman .1 1l7/68.5

OTHER PUBLICATIONS IBM Tech. Disc. Bulletin, Vol. 9, No. 7, Dec. 1966, Lubricants for Magnetic Recording Media, by Friedman et al.

Primary ExaminerWilliam R. Trenor Attorney, Agent, or FirmCharles B. Cannon [57] ABSTRACT Phosphorescent and fluorescent coated sheets and films and coating compositions and methods for making the same in which the coating compositions include a solid phase embodying a phosphorescent pigment and/or fluorescent pigment phase and a so-called hot melt coating or vehicle for the pigment. The coating compositions are applied to a carrier or base sheet by a continuous coating operation, at an elevated temperature, following which the coating composition is transferred from the carrier or base sheet to a polyester or like film, or to a paper sheet or woven fabric, on which it is carried to complete the phosphorescent and/or fluorescent coated film. The phosphorescent products are useful as label stock, highway warning signs and road stripes, identification tapes, which glow at night, on tags, games, clock faces, instrument dial faces and for other purposes and the fluorescent products are useful in the graphic art fields and elsewhere. The continuous coating operation is much more rapid than prior art processes and avoids the use of highly volatile solvents employed in that process and the industrial pollution and other hazards thereto, as well as the extended drying time of the solvents which is required in the use of such prior art methods.

Finely divided light-reflective particles, such for example, as glass beads, aluminum foil chips, metal powders and colored plastic resinous particles may also be incorporated in the new coated sheets or films by application to the hot melt coating while the latter is in a soft condition to enable the finely divided reflective particles to adhere thereto.

19 Claims, 6 Drawing Figures PATENTEU 3 51975 'SHEEI30F3 PHOSPHORESCENT, FLUORESCENT AND REFLECTIVE COATED SHEETS OR FILMS AND COMPOSITIONS AND METHOD FOR MAKING THE SAME PRIOR ART I-Ieretofore in the art of making phosphorescent and fluorescent coated sheets it has been customary to coat the base sheet or film by a silk screen or-other process which is slow and laborious and requires a drying cycle which adds materially to the expense of'making the coated sheets or films. In addition, the prior art methods involve the use of highly volatile solvents which enhance the fire hazard, pollution and other industrial hazards involved in making such products and such prior art methods have required extended drying times.

In addition, in making pigmented phosphorescent and fluorescent coated sheets or films attempts have been made to incorporate the finely divided glass beads or like finely divided particles directly in the pigmented solvent base adhesive coating on the base sheet or carrier, but this practice has not been entirely successful for the reason that in such prior art practice the glass beads or other finely divided light-reflective particles become imbedded in the adhesive coating.

Moreover, certain of the prior art coating techniques have had the further disadvantage which resides in the fact that the particles of solids embodied in viscous vehicles have tended to produce scratches in the coatings and inconsistent or non-uniform coatings, particularly in high speed operations. Furthermore, certain of such prior art coating methods have required the use of a solvent base adhesive coating as a subtrate for the pigment vehicle adhesive coating to be applied thereover.

OBJECTS An object of the present invention is to provide new and improved phosphorescent films and new and improved compositions and method for making the same.

Another object of the invention is to provide new and improved fluorescent films and new and improved compositions and method for making the same.

A further object of the invention is to provide new and improved compositions and a new and improved method for making combination phosphorescent and reflective coated sheets or films by a high speed coating operation.

An additional object of the invention is to provide a new and improved method of making phosphorescent films which are useful as label stock, highway warning signs and markers, identification tapes, which glow at night, on tags, games, clock faces, instrument dial faces and other purposes and in accordance with which new method such phosphorescent coatings'may be made by a continuous high speed coating operation at a speed which is much faster than is now possible in making phosphorescent films by prior art methods.

Another object of the invention is to provide a new and improved phosphorescent coated film which has the desirable properties of such phosphorescent films including flexibility, long shelf life. long glow life, and which can be made rapidly by a coating operation at an elevated temperature and dried without the delay incidental to the time required for curing com parable prior art coated films.

Another object of the invention is to provide a new and improved method of making phosphorescent and fluorescent reflective coated sheets having finely divided reflective particles, such as glass beads, aluminum foil chips, metal powders and colored plastic resinous particles, incorporated therein in such a manner that the desired light-reflective characteristics of the glass beads or other finely divided light-reflective materials are preserved.

Other objects will appear hereinafter.

DESCRIPTION OF DRAWINGS FIG 1 of the drawings is a diagrammatic flow sheet illustrating a typical and preferred embodiment of an apparatus and method which may be used in making the new phosphorescent and/or fluorescent coated sheets or films;

FIG. 2 is a diagrammatic view of the hot melt coater and the coating and transfer rolls embodied in the apparatus shown in FIG. 1;

FIG. 3 is a transverse sectional detail view of the hot melt coater;

FIG. 4 is a top plan view of the hot melt coater and coating roll;

FIG. 5 is a diagrammatic flow sheet similar to FIG. 1, but illustrating the manner in which the glass beads or other finely divided light-reflective particles are applied to the hot melt coated phosphorescent or fluorescent coated sheets or films in a modification of the invention; and

FIG. 6 is a diagrammatic view illustrating another coating method and apparatus which may be employed in the practice of the present invention.

DETAILED DESCRIPTION A typical and preferred example which may be followed in making the new phosphorescent coated sheets or films, according to the practice of the present invention, is illustrated in the following Example No. l, which indicates the relative weight of the composition in quantity sufficient to make a one thousand (1,000) pound batch of the coating composition having a viscosity at the temperature set forth in the example:

EXAMPLE NO. 1

In a typical and preferred composition for use in making a phosphorescent coated sheet or film, which is particularly useful for the purposes set forth above, the mixture of calcium sulfide (C) and strontium sulfide (SrS) provides the phosphorescent pigment. The silica gel acts as a dispersant for the pigment and prevents excess fall-out of the pigment from the vehicle during the coating operation; and because the silica gel is translucent to light it enables radiated light energy to penetrate to the pigment particles while. at the same time, dispersing the pigment particles and preventing the pigment particles from packing. In addition, the silica gel allows for maximum exposure of the pigment particles to light energy and resulting maximum absorption of radiated light energy and for re-emission of light energy from the phosphorescent coated film or sheet.

In the vehicle phase of the composition of Example No. 1, the petroleum wax and microcrystalline wax components harden and stiffen the resulting coating film and the polyethylene polymer component controls the body and adhesiveness of the coating which would otherwise be watery and non-usable.

In the preparation of the coating composition as set forth in the foregoing Example No. 1, the petroleum wax, the microcrystalline wax and the polyethylene polymer components of the vehicle phase and the pigment phase are heated and thoroughly mixed by agitation and blended at a temperature maintained at approximately 350F, that is, at approximately the melting point of the adhesive vehicle phase of the composition of Example No. l, at which it has a viscosity of approximately 217 cps, whereupon the powdered components of the pigment phase of the coating composition are added thereto with thorough mixing. I

The rather sharply defined melting point of the vehicle phase of the coating composition of the foregoing Example No. 1, namely, approximately 350F, insures good flowability in the resulting coating composition. In addition, the vehicle of the foregoing Example No. 1 insures translucency in the vehicle which permits ready passage of light energy into the body of phosphorescent material.

The vehicle phase of the composition, as set forth in the foregoing Example No. l, is highly desirable, particularly in that (a) it possesses low viscosity; (b) it has a sharply defined melting temperature and hence insures good flowability at low pressures and close viscosity control; and (c) it is translucent so that it readily permits passage of light energy into the body of the phosphorescent material employed in the pigment phase of the composition.

The components of the pigment phase of the composition, as set forth in the foregoing Example No. 1, should be thoroughly dried before they are mixed with and incorporated into the vehicle phase of the composition to insure complete blending of the pigment phase of the vehicle phase and complete dispersion of the'pigment phase in the vehicle phase of the composition.

A flow sheet illustrating a typical and preferred method and apparatus which may be employed in the practice of the present invention is illustrated in FIGS. 1 to 4, inclusive, of the drawings, wherein it is generally indicated at 10, and comprises a feed roll 11 for a supply or web of a flexible paper or like base or carrier sheet 12,which is preferably a paper base sheet coated with a silicone or like resin release coating. The web of paper or like base or carrier sheet 12 is directed over a set of webtensioning rolls 13, then over guide rolls 14 and 15, and thence over a coating roll 16 to which the hot melt coating composition. such as that of Example No. 1, may be applied from a hot melt coater unit 17. A suitably heated hot melt tank or supply reservoir 18 may be provided in which the hot melt coating composition may be kept in a fluid condition at a temperature of approximately 350F and supplied to the hot melt coater unit 17 by way of a hose or pipeline 19. An air pressure regulator or valve 35 is provided in the line 19 and this valve 35 is connected to an air line 36, which, in turn, is connected to a tank 37 of compressed air.

As shown in FIGS. 2 and 3 of the drawings, the coater unit 17 is in the form of a triangular-shaped receptacle having a discharge outlet or slot 20 at its lower end or apex (FIG. 3) from which the hot melt coating composition is supplied by gravity to the coating roll 16. The coating roll 16 and the hot melt coater unit 17 may be of any desired length such, for example, as 24 inches, depending upon the width of the carrier base sheet 12 and the sheet or film to be coated. The discharge slot 20 may be of varying widths, depending upon the desired thickness of the coating, but a discharge slot 20 of from 10 to 12 mils in width had been found satisfactory for providing a coating of the phosphorescent coating material of Example No. l of 10 mils in thickness.

A feed roll 21 carries a supply or web or polyester or like film, flexible paper sheet or the like, and the polyester film 22 or the like, works over a set of webtensioning rolls 34, then over guide rolls, as 23, and thence between a pair of laminating rolls 24 and 25, which are initially maintained at room temperature, and by which the coating composition is transferred from the carrier or base sheet 12 to the supporting polyester film 22 or the like. The silicone-treated base or carrier and coated sheet 12 is laminated to one surface of the polyester supporting film 22 or the like and the resulting composite laminated sheetfilm is generally indicated at 26.

The temperature of the pigment adhesive coating composition of Example No. 1, as applied from the coater unit 12 to the coating roll 16 is critical within the range herein specified, and should be maintained at an optimum temperature of approximately 350F with a permmisible variation of not in excess of 50F, plus or minus 5F. Thus, if the melting point of the hot melt phase of the pigment adhesive coating composition, as applied to the coating roll 16 and thence to the polyester film 22, paper sheet or the like, is substantially below 300F the resulting pigment adhesive coating composition will be too viscous and will not flow readily and hence, will greatly impede the speed of production of the flexible coated polyester or like flexible film or sheet product, whereas, on the other hand, if the melting point of the adhesive phase of the pigment adhesive coating composition, as applied from the coater unit 17 to the coating roll 16 and thence to the polyester film 22, or the like, is substantially in excess of 400F, the adhesive vehicle phase of the coating composition will degrade and the components thereof separate and the adhesive vehicle phase of the coating composition will tend to decompose with resultant damage to the flexible coated film or sheet.

Moreover, the viscosity of the adhesive phase of the pigment adhesive coating compositions of the present invention, as set forth in the foregoing Example No. 1, and in the following examples, is critical and should be maintained between 217 and 1,100 cps at the temperature stated to assure low viscosity and full flowability of the pigment adhesive coating compositions at low pressure differentials.

The laminated composite sheet-film 26 is then passed over a so-called chill or cooling roll 27, which is preferably maintained at a temperature of approximately 60F, as by recirculating cold tap water therethrough,

so as to cool the composite laminated sheet-film 26 to approximately the same temperature, that is, to a temperature of approximately 60F. The cooled and composite laminated sheet-film 26 is then passed over guide rolls, as 28-29, and thence over delaminating rolls 30 by which the silicone resin coated carrier or base sheet 112 is delaminated from the polyester resin coated film 22 with the phosphoresent coating of Example No. l retained by and upon the completed polyester resin film 22, which is then passed over a guide roll 31 and thence to a take-up roll 32 for the completed coated polyester film, the delaminated silicone-treated paper carrier or sheet 12 being fed from the delaminating rolls 30 to a take-up roll 33 for reuse.

A pan-lil e receptacle 38 is arranged below the coating roll 16 and has a drain outlet 39 attached thereto and in the use of the apparatus as shown in FIGS. 1 to 4, inclusive, the pan-like receptacle 38 acts as a waste receptacle for the hot melt coating material which may drip from the coating roll 16.

If any when necessary, and residual coating material may be removed from the coater unit 17-20 by opening the air valve 35 in the line 19 and passing compressed air therethrough from the compressed air storage tank or reservoir 37, line 36, air valve 35 and through the coater unit 17 from which any residual coating materials may be discharged into the waste receptacle or pan 38.

Additional examples of compositions suitable for use in preparing the new phosphorescent coated films in accordance with the present invention, and following the same general procedure as is set forth in reference to the foregoing Example No. l, are set forth in the following examples:

EXAMPLE NO. 2

Quantity Pigment Phase: in Pounds (l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) 100 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 50 Vehicle Phase:

Ethylene vinyl acetate copolymer (slab) 850 (viscosity of 430 cps at MP of 350F) TOTAL 1,000

EXAMPLE NO. 3

Quantity Pigment Phase: in Pounds l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) 100 (2) Silica gel (dispersant)(powder) (AEROGEL Monsanto) 50 Vehicle Phase:

(Low Density)Polyethylene copolymer (pellets) 850 (viscosity of [.000 cps at MP of 375F) TOTAL l .000

EXAMPLE NO. 4

Quantity Pigment Phase: in Pounds (l Mixture of calcium sulfide (C218) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) I00 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 50 Vehicle Phase:

Polypropylene (HERCULES coating powder) 850 (viscosity of l 100 cps at MP. of 330F) TOTAL 1,000

EXAMPLE NO. 5

Quantity Pigment Phase: in Pounds (l) Mixture of calcium sulfide (Q15) and strontium sulfide (SrS)(powder) (HELCON U.S. Radium Co.) 100 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 50 Vehicle Phase:

Mixture of parafiin wax (slab) and polyethylene polymer (pellets) 850 (viscosity of 200 cps at MP. of 325F) TOTAL 1,000

EXAMPLE NO. 6

Quantity Pigment Phase: in Pounds (l) Mixture of calcium sulfide (C215) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) 103 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 37 Vehicle Phase:

(1) Petroleum wax(slab) 54l (2) Microcrystalline wax(slab) I06 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 217 cps at MP. of 350F) TOTAL 1000 EXAMPLE NO. 7

Quantity Pigment Phase: in Pounds (l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 60 Vehicle Phase:

( l Petroleum wax(slab) 54! (2) Microcrystalline waxtslah) I06 (3) Polyethylene polymert pellets) 203 Total 850 850 (viscosity of 2l7 cps at MP. of 350F) TOTAL l .000

EXAMPLE NO. 8

Pigment Phase:

(1) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.)

(2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) Vehicle Phase:

(1) Petroleum wax(s1ab) 541 (2) Microcrystalline wax(slab) 106 (3) Polyethylene polymer( pellets) 203 Total 850 (viscosity of 217 cps at MP. of 350F) TOTAL EXAMPLE NO. 9

Pigment Phase:

(l) Mixture of calcium sulfide (C218) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.)

(2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) Vehicle Phase:

(1) Petroleum wax(s1ab) 541 (2) Microcrystalline wax(slab) 106 (3) Polyethylene polymer( pellets) 203 Total 850 (viscosity of 217 cps at M.P.'of 350F) TOTAL EXAMPLE NO. 10

Pigment Phase:

(1) Mixture of calcium sulfide (C215) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.)

(2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) Vehicle Phase:

(1) Petroleum wax(s1ab) 541 (2) Microcrystalline wax(s1ab) 106 (3) Polyethylene polymer(pe11ets) 203 Total 850 (viscosity of 217 cps at MP of 350F) TOTAL Typical and preferred examples of compositions which may be employed in the practice of the present invention, in making fluorescent coated sheets or film, following the method illustrated in the drawings, are

illustrated in the following examples:

EXAMPLE NO. 11

Pigment Phase:

(1) Mixture of zinc sulfide (ZnS and cadmium sulfide (CdS) (powder) (2) Silica gel (dispersant)(powder) (AEROGEL Monsanto) Vehicle Phase:

(1) Petroleum wax(slab) 541 2) Microcrystalline wax(slab) 106 3) Polyethylene polymefl pellets) 203 Total 850 EXAMPLE NO. 1 l-Continued Quantity Quantity m Pounds Pigment Phase: in Pounds 5 (viscosity of 217 cps at MP of 350F) TOTAL 1,000 104 EXAMPLE NO. 12

Quantity 850 Pigment Phase: in Pounds l 000 (1 Mixture of zinc sulfide (ZnS) and l cadmium sulfide (CdS) (powder) 100 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto 50 Vehicle Phase: Ethylene vinyl acetate copolymer(s1ab) 850 Y (viscosity of 430 cps at MP. of 350F) Pwnds TOTAL 1000 EXAMPLE NO. 13 15 Quantity Pigment Phase: in Pounds (1) Mixture of zinc sulfide (ZnS) and 850 cadmium sulfide (CdS) (powder) 100 (2) Silica gel (dispersant) (powder) 1,000 (AEROGEL Monsanto) 50 Vehicle Phase:

Polyethylene copo1ymer( pellets) 850 (viscosity of 1000 cps at MP. of 375F) TOTAL 1,000

Quantity in Pounds EXAMPLE NO. 14 127 Quantity 23 Pigment Phase: in Pounds (1 Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 100 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 850 l 000 Vehicle Phase:

Polypropylene (HERCULES coating powder) 850 50 (viscosity of 1 100 cps at MP of 330F) TOTAL 1,000

EXAMPLE NO. 15'

Quantity Pigment Phase: in Pounds Q a tit (1 Mixture of zinc sulfide (ZnS) and in Pounds cadmium sulfide (CdS) (powder) 100 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 50 100 5 Vehicle Phase:

0 Mixture of paraffin wax(s1ab) and polyethylene polymeflpellets) 850 (viscosity of 217 cps at MP. of 325F) TOTAL 1.000

EXAMPLE NO. 16

Quantity Pigment Phase: in Pounds (l Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 1 l3 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 37 Vehicle Phase:

(1) Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) I06 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 217 cps at M.P. of 350F) TOTAL L000 EXAMPLE No. 17

Quantity Pigment Phase: in Pounds (l) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 90 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 60 Vehicle Phase:

(1) Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) I06 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 2l 7 cps at M.P. of 350F) TOTAL 1,000

EXAMPLE NO. 18

Quantity Pigment Phase: in Pounds (l) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) l04 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 46 Vehicle Phase:

(I) Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) 106 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 2l 7 cps at M.P. of 350F) TOTAL l,000

EXAMPLE NO. 19

Quantity Pigment Phase: in Pounds (l) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) l35 (2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) Vehicle Phase:

(l) Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) 106 (3) Polyethylene polymer( pellets) 203 Total 850 850 (viscosity of 217 cps at MP. of 350F) I TOTAL L000 EXAMPLE NO. 20

Quantity Pigment Phase: in Pounds l Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 127 2) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 23 Vehicle Phase:

(1) Petroleum wax(slab) 54l (2) Microcrystalline wax(slab) I06 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 2l7 cps at M.P. of 350F) TOTAL L000 Typical and preferred compositions which may be employed in the practice of the present invention, in making a coated sheet or film which has both phosphorescent and fluoroescent properties, in accordance with the method illustrated in the drawings, are illustrated in the following examples:

EXAMPLE NO. 21

Quantity Pigment Phase: in Pounds (l Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) 50 (2) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 50 (3) Silica gel (dispersant) (powder) (AEROGEL Monsanto) 50 Vehicle Phase:

(1 Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) l06 (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 217 cps at MP. of 350F) TOTAL 1,000

EXAMPLE NO. 22

Quantity Pigment Phase: I in Pounds (l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) 50 (2) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 50 (3) Silica el (dispersant) (powder) (AER GEL Monsanto) 50 Vehicle Phase: Ethylene vinyl acetate copolymer(slab) 750 Copolymer of styrene and isobutylene (KLYRVEL Velsicol Co.. Chgo.,lll.)

a Total 850 850 (viscosity of 1.000 cps at M.P. of 350F) TOTAL 1000 EXAMPLE NO. 23

Quantity Pigment Phase: in Pounds l Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co) 50 (2) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 50 (3) Silica gel (dispersant) (powder) EXAMPLE NO. 23-C0ntinued EXAMPLE NO. 27

Quantity Quantity Pigment Phase: in Pounds Pigment Phase: in Pounds 5 (AEROGEL Monsanto) 50 l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) M (HELCON U.S. Radium C0.) 52 g y y pg y fl ge t l 750 (2) Mixture OfZirlC sulfide (ZnS) and P y 0 yrene Y ene cadmium sulfide (CdS) (powder) 52 (KLYRVEL 90 Velsicol Co.,Chgo.,lll:) 100 3 Sili l (dispersant) (powder) Total 850 850 I0 (AEROGEL Monsanto) 46 't f 4 (viscosi y o l 000 cps at M P of 00 F) TOTAL L000 Vehicle Phase:

(I) Petroleum wax(slab) 541 (2) Microcrystalline wax(slab) I06 (3) Polyethylene polymer( pellets) 203 Total 850 850 (viscosity of 2l7 cps at MP. of 350F) TOTAL L000 Quantity Pigment Phase: in Pounds (l Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) EXAMPLE 28 (HELCON U.S. Radium Co.) 50 (2) Mixture of zinc sulfide (ZnS) and Quantity cadmium sulfide (CdS) (powder) 50 s (3) Silica gel (dispersant) (powder) Pigment Phdsc' m Pounds (AEROGEL Monsanto) 50 (l) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) M (HELCON us. Radium Co.) 67.5 yp py P y (HERC U LE5 750 2 Mixture of zinc sulfide (ZnS) and p b t I cadmium sulfide (CdS) (po der) 67.5

opo ymer o s yrene an 150 u y ene 3 ST 1 t d (KLYRVEL 90 Velsicol 00., Chgo..lll.) 100 'EE e i ifg g ig) Cr) 15 Total 850 L 4 (viscosity of 1 I00 cps at MP of 330F) m TOTAL 1,000 (l Petroleum wax(slab) 54] (2) Microcrystalline wax(slab) I06 (3) Polyethylene p0lymer(pellets) 203 Total 850 850 EXAMPLE NO. 25 (viscosity of2l7 cps m MP. of 350F) 3 5 TOTAL L000 Quantity Pigment Phase: in Pounds (l) Mixture of calcium sulfide (CaS) and EXAMPLE 29 strontium sulfide (SrS) (powder) (HELCON U.S. Radium Co.) 50 40 Quanmy (2) Mixture of zinc sulfide (ZnS) and A cadmium sulfide (CdS) (powder) 50 Plgmem Phase m Pounds (3) Silica gel (dispersant) (powder) (l) Mixture of calcium sulfide (CaS) and (AEROGEL Monsanto) 5O strontium sulfide (SrS) (powder) y (HELCON U.S: Radium Co.) 63.5 M (2) Mixture of zinc sulfide (ZnS) and Mixture of paraffin wax(slab) and admi m sulfide (CdS) (powder) 63.5 P y y P y (Pellets) 850 (3) Silica gel (dispersant) (powder) (viscosity of 217 cps at MP of 325F) (AEROGEL Monsanto) 23 TOTAL L000 Vehicle Phase: (l) Petroleum wax(slab) 54] (2) Microcrystalline wax(slab) 106 EXAMPLE NO 26 (3) Polyethylene polymer( pellets) 203 Total 850 850 (viscosity of 217 cps at MP. of 350F) Quantity Pigment Phase: in Pounds TOTAL L000 (l) Mixture of calcium sulfide (((IiaS) and 55 strontium sulfide (SrS) (pow er) (HELCON us. Radium Co.) 45 EXAMPLE 30 (2) Mixture of zinc sulfide (ZnS) and cadmium sulfide (CdS) (powder) 45 (3) Silica gel (dispersant) (powder) 1 Ph, 5- (AEROGEL Monsanto) 60 Vehicle phase; (I) Mixture of calcium sulfide (CaS) and strontium sulfide (SrS) (powder) Webb) (HELCON us. Radium Cu) ms (2) Mlcmcrysmnme 'axislab) (2) Mixture of Zinc sulfide (ZnS) and fl L cadmium sulfide (CdS) (powder) 07.5

Total 850 850 (3) Silica gel (dispersant) (powder) (viscosity of 2| 7 cps at MP. of 350F) (AEROGEI. Monsanto) l5 TOTAL L000 Vehicle Phase: l Petroleum wax(sliib) 541 (2) Microcrystalline \\'ax(slah) I06 EXAMPLE NO. 30-Continued Quantity Pigment Phase: in Pounds (3) Polyethylene polymer(pellets) 203 Total 850 850 (viscosity of 217 cps at M.P. of 350F) TOTAL 1,000

MODIFICATION EMPLOYING LIGHT-REFLECTIVE GLASS BEADSOR LIKE FINELY DIVIDED LIGHT-REFLECTIVE MATERIAL (FI G.5)

In a modification of the present invention as described above, finely divided light-reflective materials in the form of small glass beads or other finely divided light-reflective particles, such as aluminum foil chips, metal powders and colored or white plastic particles, may be incorporated in the new flexible phosphorescent and/or fluorescent coated sheets or films by means of the apparatus illustrated in the drawings, and without incorporating or fully embedding such glass beads or other finely divided light-reflective material directly into the coating compositions, with the resultant advantages referred to hereinafter.

The modification of the invention as used for making the new flexible phosphorescent and/or fluorescent coated sheets or films having small glass beads or other finely divided lightreflective particles or material incorporated therein is illustrated in FIG. 5 of the drawings in which those parts of the apparatus illustrated, which correspond to similar parts illustrated in FIGS. 1 to 4, inclusive, have been given similar reference numerals followed by the additional and distinguishing reference character a.

Thus, in the practice of the modified form of the invention illustrated in FIG. 5, after the flexible polyester film, paper sheet, or the like, has been coated with one or another of the pigment adhesive coating compositions set forth in Examples Nos. 1 to 30, inclusive, the supply reservoir or hopper 18a may be emptied of all of the pigment adhesive coating composition used in the preceding coating operation and the supply reservoir or hopper 18a may then be filled with small lightreflective glass beads or other finely divided lightreflective material or particles such, for example, as aluminum foil chips, metal powders or white or colored plastic resinous particles and any residual coating material in the coater-applicator unit 170 may be removed therefrom by opening the air valve 35a in the line 36a and blowing compressed air through the line 19a and coater applicator 17a-20a so as to discharge any residual coating material from the coater-applicator unit l7a-20a into the waste receptacle or pan 38a. The coated polyester film 22a may then be removed from the take-up roll 32a and passed through the webtensioning rolls 13a thence over the guide rolls l4a-l5a, and thence over the coating or applicator roll 16a at which the small light-reflective beads or other finely divided light-reflective material or particles may be applied to the pigmented adhesive coated polyester film 22 from the storage reservoir or hopper 180 by way of a supply line 19a and the coater or applicator unit l7a-20a. During this operation, the pigment adhesive coating on the polyester film 22, paper sheet or the like, is maintained sufficiently soft and tacky by the laminating rolls 24 and 25 which have been heated by the previous coating operations, so as to enable the small glass beads or other finely divided light-reflective material or particles to adhere to the outer surface of the pigment adhesive coating without being embedded therein or covered or fully coated thereby. During this operation any excess of the small glass beads or like light-reflective particles will drop by gravity from the applicator roll 25a into the waste receptacle or pan 38a.

It will be noted, in this connection, that the quantity of the small glass beads or other finely divided lightreflective material or particles which will adhere to the pigment adhesivecoated polyester film 22 is determined by the linear speed of the polyester film 22a or the like, and the degree of agitation of the small glass beads or like finely divided light-reflective materials or particles as the same are applied to the tacky polyester film from the discharge outlet or slot 20a of the coater or applicator unit 17a-20a; any excess of the small glass beads or like finely divided light-reflective material or particles which does not adhere to the polyester films 22a merely falling therefrom by gravity at the point 20a into the waste receptacle or pan 38a.

In the practice of the form of the present invention, as illustrated in FIG. 5, a vibrator unit 40 of conventional design is mounted under the coater-applicator unit l7a-20d so as to vibrate the coater-applicator unit -2041 and thus enhance the flow of glass beads or other finely divided light-reflective particles therefrom onto the applicator roll 25a. To this end the coaterapplicator unit l7a-20a may be pivotally or rockably mounted as at 41 (FIG. 5).

After the glass beads or other finely divided lightreflective particles have thus been applied to the coated film or sheet 32a the thus completed film or sheet 42 is passed over a chilling or cooling roll 27a and a guide roll 28a, and thence is wound on a take-up roll 32a from which it may be withdrawn for use.

lt should be further noted, in this connection, that the new method of making the phosphorescent and/or fluorescent coated flexible sheets or films 22-22a having small glass beads or like finely divided light-relective material or particles incorporated thereon has the advantage over prior art methods which resides in the fact that it is not practical to incorporate such lightreflective glass beads or like finely divided lightreflective material or particles directly into the pigment adhesive coating for the reason that if this is done the small glass beads or like finely divided light-reflective material or particles become embedded in and fully covered or coated by the pigment adhesive coating and their desired reflectivity is materially inhibited, whereas in the practice of the present invention, the small glass beads or other finely divided light-reflective material or particles are adhered to the outer surface of the tacky pigment adhesive coating but are not embedded therein and are not completely coated or covered thereby and thus maintain their desired reflectivlty.

A preferred form of the glass beads which may be employed in the practice of the present invention is one in which the glass beads have the following characteristics:

colored, as desired MODIFICATION ILLUSTRATED IN FIG. 6

Another modified form of apparatus and method 10 which may be employed in the practice of the present invention are illustrated in FIG. 6 of the drawings in which those parts of the invention which are similar to or correspond to parts in the form of the apparatus illustrated in FIGS. 1 to 4, inclusive, have been given the same reference numerals followed by the additional and distinguishing reference character b.

The form of the apparatus and the method employed in the practice of the present invention, as illustrated in FIG. 6, differs from the form of the apparatus and method illustrated in FIG. 1 in that the hot melt adhesive coating material is applied to the flexible paper or like flexible base or carrier sheet 12b from a pan-like receptacle 43 having an open top and to which the hot melt adhesive coating is supplied by a pipe or line 44 from'a heated hot melt storage or supply reservoir 45, and thence to the coating roll 16); adjacent to which a doctor roll 46 is provided.

Thus, in this form of the invention illustrated in FIG. 6, the coating roll 16b dips into or works in the body of hot melt coating in the pan-like receptacle 43 and the hot melt adhesive coating is applied by the coating roll 16b to the flexible film or paper, or like flexible base or carrier sheet 12b following which the procedure involved in the practice of the invention, as illustrated in FIG. 6, is similar to that illustrated in FIG. 1, and which has been described hereinbefore.

It will thus be seen from the foregoing description, considered in conjunction with the drawings, that the present invention provides new and improved coated sheets or films having phosphorescent properties; new and improved coated sheets or film having fluorescent properties; new and improved coated sheets or films having both phosphorescent and fluorescent properties; new and improved coated sheets or films having phosphorescent and/or fluorescent and light-reflective properties; and new and improved compositions and methods for making such coated sheets or films.

We claim:

1. The method of making a flexible coated film or sheet which comprises the steps of:

a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase selected from the group consisting of phosphorescent and fluorescent pigments, and mixtures thereof, and an adhesive vehicle phase;

I. the said adhesive vehicle phase of the said coating composition having a melting point of not substantially higher than 405F and not substantially lower than 295F and having a viscosity within the aforesaid temperature range of between 2l7 and l.l00 cps;

b. applying the aforesaid pigment adhesive coating composition within the aforesaid temperature and viscosity ranges to a flexible film base or carrier sheet;

c. transferring the aforesaid pigment adhesive coating composition while it is in a molten state, from the said flexible film base or carrier sheet to a flexible supporting film or sheet to complete the said flexible coated film or sheet; and then (d) cooling the flexible supporting film or sheet with the said pigment adhesive coating thereon in order to solidify said pigment adhesive coating. 2. The method defined in claim 1 in which a. the said flexible film base or carrier sheet and the said flexible supporting film or sheet are laminated to laminate the said flexible film base or carrier sheet and the said flexible supporting film or sheet together and thus transfer the said pigment adhesive coating white it is in a matter state from the said flexible film base or carrier sheet to the said flexible supporting film or sheet. 3. The method defined in claim 2 which comprises passing the said flexible film base or carrier sheet over a coating roll while applying the said pigment adhesive coating thereto.

4. The method defined in claim 3 in which (a) the said flexible supporting film or sheet with the said pigment adhesive coating thereon is cooled in order to solidify said pigment adhesive coating, and then said flexible supporting film or sheet is delaminated from the said flexible film base or carrier sheet.

5. The method defined in claim 4 in which a. the delamination of the said coated flexible supporting film or sheet from the said flexible film base or carrier sheet is effected by l. chilling the laminated flexible film base or carrier sheet and the said flexible supporting film or sheet; and

2. then effecting delamination of the pigment adhesive coated flexible supporting film or sheet from the said flexible film base or carrier sheet.

6. The method of making a flexible coated film or sheet which comprises the steps of:

a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase in the form of a phosphorescent pigment selected from the group consisting of calcium sulfide and strontium sulfide and fluorescent pigment selected from the group consisting of zinc sulfide and cadmium sulfide, and mixtures thereof, and silica gel as a dispersant, with an adhesive vehicle phase comprised of one or more materials selected from the group consiting of l) a mixture of petroleum wax, microcrystalline wax and polyethylene polymer; (2) ethylene vinyl acetate copolymer; (3) polyethylene copolymer; (4) polypropylene; (5) a mixture of paraffin wax and polyethylene polymer; and (6) a copolymer of styrene and isobutylene; l. the said adhesive vehicle phase of the said coating composition having a melting point of not substantially higher than, 405F and not substantially lower than 295F and having a viscosity within the aforesaid temperature range of between 217 and l,l00 cps;

b. applying the said pigment adhesive coating composition within the temperature range and within the viscosity range stated and while it is in a molten state to a flexible release-coated film base or carrier sheet;

c. laminating the said release-coated flexible film base or carrier sheet to a flexible supporting film or sheet to transfer the said pigment adhesive coating to the said flexible supporting film or sheet;

d. cooling the flexible supporting film or sheet with the said pigment adhesive coating thereon in order to solidify said pigment adhesive coating; and

e. delaminating the said flexible supporting film or sheet with the said pigment adhesive coating thereon from the said flexible film base or carrier sheet.

7. The method defined in claim 6 in which a. the said adhesive vehicle phase of the said coating composition is heated to a temperature of not substantially higher than 405F nor substantially lower than 295F to melt the said adhesive vehicle phase of the said coating composition before the said pigment phase is added thereto.

8. The method defined in claim 6 in which a. the said flexible coated supporting film or sheet is heated to soften and render tacky the outer surface of the said pigment adhesive coating thereon; and in which b. a finely divided light-reflective material selected from the group consisting of small glass beads, finely divided aluminum foil chips, finely divided metal powders and finely divided plastic resinous particles, is applied and adhered to and exposed on the heated and softened outer surface of the said flexible coated supporting film or sheet while it is in a tacky condition without completely embedding the said finely divided materials in the body of the said pigment adhesive coating.

9. The method of making a flexible coated film which comprises the steps of:

a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase selected from the group consisting of phosphorescent and fluorescent pigments, and mixtures thereof, and an adhesive vehicle phase;

1. the said adhesive vehicle phase of the said coating composition having a melting point of not substantially higher than 405F and not substantially lower than 295F and having a viscosity within the aforesaid temperature range of between 217 and 1,100 cps; and

b. applying the aforesaid pigment adhesive coating composition within the aforesaid temperature and viscosity ranges and while it is in a molten state, to a flexible film base or carrier sheet to complete the said flexible coated film or sheet.

10. The method defined in claim 9 in which a. the said flexible coated film or sheet is heated to soften and render tacky the outer surface of the said pigment adhesive coating thereon; and in which b. a finely divided light-reflective material is applied and adhered to and exposed on the heated and soft ened outer surface of the said flexible coated film or sheet while it is in a tacky condition without completely embedding the said finely divided lightreflective material in the body of the said pigment adhesive coating.

11. The method of making a flexible coated film or sheet which comprises the steps of:

a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase 11 in the form of a phosphorescent pigment selected from the group consisting of calcium sulfide and strontium sulfide and fluorescent pigment selected from the group consisting of zinc sulfide and cadmium sulfide, and mixtures thereof, and silica gel as a dispersant, with an adhesive vehicle phase comprised of one or more materials selected from the group consisting of l a mixture of petroleum wax, microcrystalline wax and polyethylene polymer; (2) ethylene vinyl acetate copolymer; (3)

polyethylene copolymer; (4) polypropylene; (5) a mixture of paraffin wax and polyethylene polymer;

and (6a copolymer of styrene and isobutylene; l. the said adhesive vehicle phase of the said coating composition having a melting point of not substantially higher than 405F and not substantially lower than 295F and having a viscosity within the aforesaid temperature range of between 217 and 1,100 cps; b. applying the said pigment adhesive coating corn position within the temperature range and within the viscosity range stated and while it is in a molten state to a flexible release-coated film base or carrier sheet; c. laminating the said release-coated flexible film base or carrier sheet to a flexible supporting film or sheet to transfer the said pigment adhesive coating to the said flexible supporting film or sheet; d. cooling said flexible supporting film or sheet with the said pigment adhesive coating thereon in order to solidify said pigment adhesive coating; e. delaminating the said flexible supporting film or sheet with the said pigment adhesive coating thereon from the said flexible film base or carrier sheet; f. heating the said flexible coated supporting film or sheet to soften and render tacky the outer surface of the said pigment adhesive coating thereon; and in which g. a finely divided light-reflective material is applied and adhered to and exposed on the heated and softened outer surface of the said flexible coated supporting film or sheet while it is in a tacky condition without completely embedding the said finely divided light-reflective material in the body of the said pigment adhesive coating. 12. A product prepared according to the process of claim 1.

13. A product prepared according to the process of claim 2.

14. A product prepared according to the process of claim 5.

15. A product prepared according to the process of claim 6.

16. A product prepared according to the process of claim 7.

17. A product prepared according to the process of claim 8.

118. A product prepared according to the process of claim l0.

19. A product prepared according to the process of 

1. THE METHOD OF MAKING A FLEXIBLE COATED FILM OR SHEET WHICH COMPRISES THE STEPS OF: A. FORMING A PIGMENT ADHESIVE COATING COMPOSITION BY INTIMATELY MIXING A FINELY DIVIDED PIGMENT PHASE SELECTED FROM THE GROUP CONSISTING OF PHOSPHORESCENT AND FLUORESCENT PIGMENTS, AND MIXTURES THEREOF, AND AN ADHESIVE VEHICLE PHASE;
 1. THE SAID ADHESIVE VEHILCE PHASE OF THE SAID COATING COMPOSITION HAVING MELTING POINT OF NOT SUBSTANTIALLY HIGHER THAN 405*F AND NOT SUBSTANTIALLY LOWER THAN 295*F AND HAVING A VISCOSITY WITHIN THE AFORESAID TEMPERATURE RANGE OF BETWEEN 217 AND 1,100 CPS; B. APPLYING THE AFORESAID PIGMENT ADHESIVE COATING COMPOSITION WITHIN THE AFORESAID TEMPERATURE AND VISCOSITY RANGES TO A FLEXIBLE FILM BASE OR CARRIER SHEET; C. TRANSFERRING THE AFORESAID PIGMENT ADHESIVE COATING COMPOSITION WHILE IT IS IN A MOLTEN STATE, FROM THE SAID FLEXIBLE FILM BASE OR CARRIER SHEET TO A FLEXIBLE SUPPORTING FILM OR SHEET TO COMPLETE THE SAID FLEXIBLE COATED FILM OR SHEET; AND THEN (D) COOLING THE FLEXIBLE SUPPORTING FILM OR SHEET WITH THE SAID PIGMENT ADHESIVE COATING THEREON IN ORDER TO SOLIDIFY SAID PIGMENT ADHESIVE COATING.
 2. The method defined in claim 1 in which a. the said flexible film base or carrier sheet and the said flexible supporting film or sheet are laminated to laminate the said flexible film base or carrier sheet and the said flexible supporting film or sheet together and thus transfer the said pigment adhesive coating white it is in a matter state from the said flexible film base or carrier sheet to the said flexible supporting film or sheet.
 2. then effecting delamination of the pigment adhesive coated flexible supporting film or sheet from the said flexible film base or carrier sheet.
 3. The method defined in claim 2 which comprises passing the said flexible film base or carrier sheet over a coating roll while applying the said pigment adhesive coating thereto.
 4. The method defined in claim 3 in which (a) the said flexible supporting film or sheet with the said pigment adhesive coating thereon is cooled in order to solidify said pigment adhesive coating, and then said flexible supporting film or sheet is delaminated from the said flexible film base or caRrier sheet.
 5. The method defined in claim 4 in which a. the delamination of the said coated flexible supporting film or sheet from the said flexible film base or carrier sheet is effected by
 6. The method of making a flexible coated film or sheet which comprises the steps of: a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase in the form of a phosphorescent pigment selected from the group consisting of calcium sulfide and strontium sulfide and fluorescent pigment selected from the group consisting of zinc sulfide and cadmium sulfide, and mixtures thereof, and silica gel as a dispersant, with an adhesive vehicle phase comprised of one or more materials selected from the group consiting of (1) a mixture of petroleum wax, microcrystalline wax and polyethylene polymer; (2) ethylene vinyl acetate copolymer; (3) polyethylene copolymer; (4) polypropylene; (5) a mixture of paraffin wax and polyethylene polymer; and (6) a copolymer of styrene and isobutylene;
 7. The method defined in claim 6 in which a. the said adhesive vehicle phase of the said coating composition is heated to a temperature of not substantially higher than 405*F nor substantially lower than 295*F to melt the said adhesive vehicle phase of the said coating composition before the said pigment phase is added thereto.
 8. The method defined in claim 6 in which a. the said flexible coated supporting film or sheet is heated to soften and render tacky the outer surface of the said pigment adhesive coating thereon; and in which b. a finely divided light-reflective material selected from the group consisting of small glass beads, finely divided aluminum foil chips, finely divided metal powders and finely divided plastic resinous particles, is applied and adhered to and exposed on the heated and softened outer surface of the said flexible coated supporting film or sheet while it is in a tacky condition without completely embedding the said finely divided materials in the body of the said pigment adhesive coating.
 9. The method of making a flexible coated film which comprises the steps of: a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase selected from the group consisting of phosphorescent and fluorescent pigments, and mixtures thereof, and an adhesive vehicle phase;
 10. The method defined in claim 9 in which a. the said flexible coated film or sheet is heated to soften and render tacky the outer surface of the said pigment adhesive coating thereon; and in which b. a finely divided light-reflective material is applied and adhered to and exposed on the heated and softened outer surface of the said flexible coated film or sheet while it is in a tacky condition without completely embedding the said finely divided light-reflective material in the body of the said pigment adhesive coating.
 11. The method of making a flexible coated film or sheet which comprises the steps of: a. forming a pigment adhesive coating composition by intimately mixing a finely divided pigment phase in the form of a phosphorescent pigment selected from the group consisting of calcium sulfide and strontium sulfide and fluorescent pigment selected from the group consisting of zinc sulfide and cadmium sulfide, and mixtures thereof, and silica gel as a dispersant, with an adhesive vehicle phase comprised of one or more materials selected from the group consisting of (1) a mixture of petroleum wax, microcrystalline wax and polyethylene polymer; (2) ethylene vinyl acetate copolymer; (3) polyethylene copolymer; (4) polypropylene; (5) a mixture of paraffin wax and polyethylene polymer; and (6a copolymer of styrene and isobutylene;
 12. A product prepared according to the process of claim
 1. 13. A product prepared according to the process of claim
 2. 14. A product prepared according to the process of claim
 5. 15. A product prepared according to the process of claim
 6. 16. A product prepared according to the process of claim
 7. 17. A product prepared according to the process of claim
 8. 18. A product prepared according to the process of claim
 10. 19. A product prepared according to the process of claim
 11. 